The utilization of water which contains certain inorganic impurities, and the production and processing of crude oil water mixtures containing such impurities, is plagued by the precipitation of these impurities with subsequent scale formation. In the case of water which contains these contaminants the harmful effects of scale formation are generally confined to the reduction of the capacity or bore of receptacles and conduits employed to store and convey the contaminated water. In the case of conduits, the impedance of flow is an obvious consequence. However, a number of equally consequential problems are realized in specific utilizations of contaminated water. For example, scale formed upon the surfaces of storage vessels and conveying lines for process water may break loose and these large masses of deposit are entrained in and conveyed by the process water to damage and clog equipment through which the water is passed, e.g., tubes, valves, filters and screens. In addition, these crystalline deposits may appear in, and detract from, the final product which is derived from the process, e.g., paper formed from an aqueous suspension of pulp. Furthermore, when the contaminated water is involved in a heat exchange process, as either the "hot" or "cold" medium, scale will be formed upon the heat exchange surfaces which are contacted by the water. Such scale formation forms an insulating or thermal opacifying barrier which impairs heat transfer efficiency as well as impeding flow through the system.
While calcium sulfate and calcium carbonate are primary contributors to scale formation, other salts of alkaline-earth metals and the aluminum silicates are also offenders, e.g., magnesium carbonate, barium sulfate, the aluminum silicates provided by silts of the bentonitic, illitic, kaolinitic, etc., types.
Most industrial waters contain alkaline earth metal cations, such as calcium, barium, magnesium, etc. and several anions such as bicarbonate, carbonate, sulfate, oxalate, phosphate, silicate, fluoride, etc. When combinations of these anions and cations are present in concentrations which exceed the solubility of their reaction products, precipitates form until these product solubility concentrations are no longer exceeded. For example, when the concentrations of calcium ion and carbonate ion exceed the solubility of the calcium carbonate reaction products, a solid phase of calcium carbonate will form. Calcium carbonate is the most common form of scale.
Solubility product concentrations are exceeded for various reasons, such as partial evaporation of the water phase, change in pH, pressure or temperature, and the introduction of additional ions which form insoluble compounds with the ions already present in the solution.
As these reaction products precipitate on surfaces of the water carrying system, they form scale or deposits. This accumulation prevents effective heat transfer, interferes with fluid flow, facilitates corrosive processes and harbors bacteria. This scale is an expensive problem in many industrial water systems causing delays and shutdowns for cleaning and removal.
Scale deposits are generated and extended principally by means of crystal growth; and various approaches to reducing scale development have accordingly included inhibition of crystal growth, modification of crystal growth and dispersion of the scale-forming minerals.
Many other industrial waters, while not being scale forming, tend to be corrosive. Such waters, when in contact with a variety of metal surfaces such as ferrous metals, aluminum, copper and its alloys, tend to corrode one or more of such metals or alloys. A variety of compounds have been suggested to alleviate these problems. Such materials are low molecular weight polyacrylic acid polymers. Corrosive waters of this type are usually acidic in pH and are commonly found in closed recirculating systems.
Numerous compounds have been added to these industrial waters in an attempt to prevent or reduce scale and corrosion. One such class of materials are the well known organophosphonates which are illustrated by the compounds hydroxyethylidene diphosphonic acid (HEDP) and phosphonobutane tricarboxylic acid (PBTC). Another group of active scale and corrosion inhibitors are the monosodium phosphinicobis (succinic acids) which are described in U.S. Pat. No. 4,088,678.
Polymeric treatments have been disclosed in U.S. Pat. Nos. 4,680,339; 4,731,419; 4,885,345 and 5,084,520. Utility for the treatments has been disclosed to be as dispersants in water treatment, scale inhibitors in industrial and natural waters, flocculants, coagulants and thickeners.
Moreover, methods of controlling calcium oxalate scale with an effective amount of a water-soluble (meth)acrylic acid/allyl ether copolymer have been disclosed in U.S. Pat. No. 4,872,995. A method for controlling silica/silicate deposition, including calcium and magnesium silicate by addition of a phosphonate and a water-soluble terpolymer of an unsaturated carboxylic acid monomer, an unsaturated sulfonic compound and an unsaturated polyalkylene oxide is disclosed in U.S. Pat. No. 4,933,090. Acrylate/acrylamide copolymers have been disclosed as useful for the inhibition of gypsum scale in flue gas desulfurization processes in U.S. Pat. No. 4,818,506.
A method of inhibiting phosphonate scale formation on and corrosion of iron containing solid surfaces in contact with industrial waters with a water-soluble zinc stabilizing polymer is disclosed in U.S. Pat. No.5,049,310. A method for preventing condensate corrosion in boilers comprising treating the condensate with a water-soluble polymeric composition comprising a an acrylic acid polymer containing acrylic acid groups in the form of amides of a water-insoluble aliphatic primary or secondary amine is disclosed in U.S. Pat. No. 4,999,161. However, there is still a need for polymeric treatments which provide an increased efficiency for corrosion and scale control.